Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
  • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
  • C07D491/10—Spiro-condensed systems
  • C07D491/107—Spiro-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
  • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
  • C07D493/10—Spiro-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1545—Six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
  • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
  • C09K9/02—Organic tenebrescent materials
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/22—Absorbing filters
  • G02B5/23—Photochromic filters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1003—Carbocyclic compounds
  • C09K2211/1007—Non-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1018—Heterocyclic compounds
  • C09K2211/1025—Heterocyclic compounds characterised by ligands
  • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
  • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1018—Heterocyclic compounds
  • C09K2211/1025—Heterocyclic compounds characterised by ligands
  • C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom

Definitions

• the present invention relates to a novel chromene compound, a precursor thereof and use of the chromene compound.
• Photochromism is the reversible function of a certain compound that it changes its color swiftly upon exposure to light including ultraviolet light such as sunlight or light from a mercury lamp and returns to its original color when it is put in the dark by stopping its exposure to light.
• a compound having this property is called "photochromic compound” and used as a material for photochromic plastic lenses which are photochromic optical articles.
• the photochromic plastic lenses develop a color of a neutral tint such as grey or brown. What color is developed depends on the photochromic compound as a matter of course, which is a very important factor.
• color shift due to the different characteristic properties of the photochromic compounds that are mixed together and a color change at the time of deterioration due to the difference in durability.
• a photochromic compound which by itself has two or more absorption wavelengths at a visible range when developing a color to develop a color of a neutral tint (to be referred to as "double peak compound” hereinafter) is important.
• chromene compound represented by the following formula (A) (refer to a pamphlet of International Laid-Open WO01/19813 ), a chromene compound represented by the following formula (B) or (C) (refer to a pamphlet of International Laid-Open WO03/025638 ), a chromene compound represented by the following formula (D) (refer to a pamphlet of International Laid-Open WO03/044022 ), a chromene compound represented by the following formula (E) (refer to the specification of US Patent No.
• chromene compounds represented by the following formula (F) (refer to a pamphlet of International Laid-Open WO05/028465 )
• chromene compounds have two absorption wavelengths at a visible range when developing a color and exhibit excellent characteristic properties.
• double peak characteristic a compound which has a higher color optical density at a yellow range (430 to 530 nm) than a color optical density at a blue range (550 to 650 nm) is desired as the double peak compound (in the double peak compound, the ratio of the yellow color optical density to the blue color optical density may be referred to as "double peak characteristic" hereinafter).
• double peak characteristic the ratio of the yellow color optical density to the blue color optical density
• chromene compound represented by the above formula (A) has practical levels of color optical density and double peak characteristic, it has room for improvement as it has a low fading speed.
• the chromene compound represented by the above formula (B), (C), (D) or (E) also has room for improvement as it does not have satisfactory double peak characteristic.
• chromene compound represented by the above formula (F) is excellent in double peak characteristic and has practical levels of color optical density and fading speed as it is a compound whose 7-position carbon atom is substituted by a specific aryl group, it has room for improvement as the end portion of its absorption spectrum (to be referred to as "absorption end” hereinafter) goes beyond 420 nm into the visible range with the result of large initial coloration.
• the inventors of the present invention conducted intensive studies to attain the above objects and found that the double peak characteristic can be enhanced, the wavelength of the absorption end can be made short and the initial coloration can be reduced by increasing the electron donating ability of the 7-position substituent in the indenonaphthopyran skeleton and also that when the electron donating ability of the 7-position substituent is increased, the fading speed and the durability become lower in proportion to this.
• the inventors thought if the above disadvantage could be improved by adjusting the electron donating ability of the 7-position substituent while retaining the above advantage and investigated the introduction of various substituents. They further investigated the substituents at the 6-position and the 8-position adjacent to the 7-position.
• the present invention is a chromene compound having a skeleton represented by the following formula (1): wherein R 1 is an electron donor group having a Hammett constant ⁇ p of less than 0, and the ring portion represented by the following formula (2) is a hetero ring: wherein X is an oxygen atom, sulfur atom or group represented by the following formula (3) which is directly bonded to the 7-position carbon atom: wherein R 2 is a hydrogen atom, hydroxyl group, alkyl group, haloalkyl group, alkenyl group, alkynyl group, cycloalkyl group, alkoxy group, aralkyl group, aryloxy group, aryl group, amino group, heterocyclic group having a nitrogen atom which nitrogen atom is a ring-membered hetero atom and bonds to the nitrogen atom in the above formula (3), cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbony
• the present invention is a photochromic curable composition which contains a chromene compound having a skeleton represented by the above formula (1) and a polymerizable monomer.
• the present invention is a photochromic optical article which has a polymer molded product containing a chromene compound having a skeleton represented by the above formula (1) dispersed therein as a constituent member.
• the present invention is an optical article having an optical substrate whose surface is at least partially coated with a polymer film as a constituent part, wherein the polymer film contains the chromene compound having a skeleton represented by the above formula (1) dispersed therein.
• the present invention is a naphthol compound represented by the following formula (8): wherein a, R 1 , R 3 , R 4 , R 7 , R 8 and a ring portion including X are as defined in the formula (6) in claim 3.
• the chromene compound of the present invention is a chromene compound having a skeleton represented by the above formula (1).
• the following substituents will be described hereinbelow.
• the group R 1 in the above formula (1) is an electron donor group having a Hammett constant ⁇ p of less than 0.
• the Hammett constant ⁇ p is defined based on the Hammett equation that quantifies the electric effect of a substituent bonded to an ⁇ electron system on the basis of the dissociation constant Ka of p-substituted benzoic acid.
• a substituent having a ⁇ p of 0 is a hydrogen atom, and a substituent having a ⁇ p of less than 0, that is, a negative number is a substituent having higher electron donating ability than the hydrogen atom.
• the group R 1 may be an aralkyl group, aryloxy group, aryl group, amino group or heterocyclic group having a nitrogen atom as a member hetero atom and bonded to the 6-position carbon atom via the nitrogen atom. These groups may be substituted by an electron donor substituent having a ⁇ p of less than 0.
• the aralkyl group, aryloxy group, aryl group, amino group or heterocyclic group having a nitrogen atom as a member hetero atom and bonded to the 6-position carbon atom via the nitrogen atom is an electron donor group having a ⁇ p of less than 0 when it has no substituent. Therefore, when these groups are substituted by an electron donating group having a ⁇ p of less than 0, they become groups having a ⁇ p of less than 0.
• the above alkyl group is generally a group having a ⁇ p of -0.20 to -0.10 and particularly preferably an alkyl group having 1 to 8 carbon atoms in the present invention.
• the cycloalkyl group is generally a group having a ⁇ p of less than 0 and particularly preferably a cycloalkyl group having 3 to 8 carbon atoms in the present invention.
• the alkoxy group is generally a group having a ⁇ p of -0.3 to -0.2 and particularly preferably an alkoxy group having 1 to 8 carbon atoms in the present invention.
• the aralkyl group is generally a group having a ⁇ p of less than 0 and particularly preferably an aralkyl group having 7 to 11 carbon atoms in the present invention.
• Preferred examples of the aralkyl group include benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group and naphthylmethyl group.
• One or more hydrogen atoms on the benzene ring of the aralkyl group may be substituted by a group having a ⁇ p of less than 0, for example, the above alkyl group, cycloalkyl group, alkoxy group, aralkyl group or aryloxy group. Since the aralkyl group having no substituent has a ⁇ p of less than 0, if the aralkyl group is substituted by a group having a ⁇ p of less than 0, it has a ⁇ p of less than 0.
• the aryloxy group is generally a group having a ⁇ p of -0.6 to -0.4 and particularly preferably an aryloxy group having 7 to 11 carbon atoms in the present invention.
• One or more hydrogen atoms on the benzene ring of the aryloxy group may be substituted by a group having a ⁇ p of less than 0, for example, the above alkyl group, cycloalkyl group, alkoxy group, aralkyl group or aryloxy group.
• the aryloxy group substituted by any one of these groups has a ⁇ p of less than 0 as well.
• the aryl group is generally a group having a ⁇ p of -0.1 to -0.01 and particularly preferably an aryl group having 6 to 14 carbon atoms in the present invention.
• One or more hydrogen atoms on the benzene ring of the aryl group may be substituted by a group having a ⁇ p of less than 0, for example, the above alkyl group, cycloalkyl group, alkoxy group, aralkyl group or aryloxy group.
• the aryl group substituted by any one of these groups has a ⁇ p of less than 0 as well.
• the amino group is generally a group having a ⁇ p of -1.00 to -0.10.
• the substituent of the secondary or tertiary amino group is preferably a group having a ⁇ p of less than 0, as typified by alkyl group and aryl group.
• the amino group substituted by any one of them has a ⁇ p of less than 0 as well.
• the heterocyclic group having a nitrogen atom as member hetero atom and bonded to the 6-position carbon atom via the nitrogen atom is generally a group having a ⁇ p of -1.00 to -0.40.
• these heterocyclic groups may have a group having a ⁇ p of less than 0 as a substituent. Examples of the substituent include alkyl groups such as methyl group.
• heterocyclic group having a substituent examples include 2,6-dimethylmorpholino group, 2,6-dimethylpiperidino group and 2,2,6,6-tetramethylpiperidino group.
• the group R 1 is preferably an electron donor group having a ⁇ p of -1.00 to -0.20 out of the groups enumerated above. More specifically, the group R 1 is preferably a hydroxyl group, or alkoxy group, aryloxy group, amino group or heterocyclic group having a nitrogen atom as a member hetero atom and bonded to the 6-position carbon atom via the nitrogen atom, the latter four having a ⁇ p of -1.00 to -0.20.
• an alkoxy group and a heterocyclic group having a nitrogen atom as a member hetero atom and bonded to the 6-position carbon atom via the nitrogen atom, all of which have a ⁇ p of -0.60 to -0.20, are particularly preferred because they improve the fading speed and initial coloration due to the absorption end. More specifically, the particularly preferred substituent is selected from methoxy group and morpholino group.
• the ring portion represented by the following formula (2) is a hetero ring including the 7-position and 8-position carbon atoms and X.
• the number of member atoms forming the hetero ring is preferably 5 to 7. That is, the number of member atoms indicates the number of atoms forming the ring and does not include the number of atoms of a substituent substituting the formed hetero ring. Since the chromene compound of the present invention forms the above hetero ring, it becomes a chromene compound having excellent photochromic properties.
• X is an oxygen atom, sulfur atom or group represented by the following formula (3) bonded to the 7-position carbon atom.
• the group R 2 is a hydrogen atom, hydroxyl group, alkyl group, haloalkyl group, alkenyl group, alkynyl group, cycloalkyl group, alkoxy group, aralkyl group, aryloxy group, aryl group, amino group, heterocyclic group having a nitrogen atom which nitrogen atom is a ring-membered hetero atom and bonds to the nitrogen atom in the above formula (3), cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group or halogen atom.
• alkyl group, cycloalkyl group, alkoxy group, aralkyl group, aryloxy group, aryl group, amino group and heterocyclic group having a nitrogen atom as a member hetero atom and bonded to the nitrogen atom in the above formula (3) via the above nitrogen atom are the same as those enumerated for the above group R 1 .
• the haloalkyl group is preferably a haloalkyl group having 1 to 8 carbon atoms as exemplified by trifluoromethyl group and 2,2,2-trifluoroethyl group.
• the alkenyl group is preferably an alkenyl group having 2 to 9 carbon atoms as exemplified by allyl group, propenyl group, 1-butenyl group and 2-butenyl group.
• the alkynyl group is preferably an alkynyl group having 2 to 9 carbon atoms as exemplified by propargyl group and 1-pentinyl group.
• the alkylcarbonyl group is preferably an alkylcarbonyl group having 2 to 9 carbon atoms as exemplified by methylcarbonyl group and ethylcarbonyl group.
• the alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 9 carbon atoms as exemplified by methoxycarbonyl group and ethoxycarbonyl group.
• halogen atom examples include fluorine atom, chlorine atom, bromine atom and iodine atom.
• X should have electron donating ability
• X is preferably an oxygen atom or a group represented by the above formula (3).
• the group R 2 is preferably a group having a Hammett constant ⁇ p of -0.20 to 1.00 as exemplified by hydrogen atom, alkyl group, haloalkyl group, cyano group, nitro group and halogen atom from the viewpoints of absorption end and fading speed.
• hydrogen atom, alkyl group, haloalkyl group and halogen atom are more preferred. More specifically, hydrogen atom, methyl group, trifluoromethyl group and fluorine atom are more preferred.
• hetero rings represented by the above formula (2) a hetero ring represented by the following formula (4) is particularly preferred so as to obtain a chromene compound having excellent photochromic properties. This preferred hetero ring will be described hereinbelow.
• the hetero ring represented by the above formula (2) is preferably a 5 to 7 membered hetero ring represented by the following formula (4).
• the skeleton represented by the above formula (1) is represented by the following formula (5).
• R 1 is as defined in the above formula (1). Therefore, preferred R 1 is the same as the group explained for the above group R 1 .
• X is as defined in the above formula (2). Therefore, preferred X is the same as the group explained for the above hetero ring.
• Y is an oxygen atom, sulfur atom or group represented by the following formula (3).
• R 2 is a hydrogen atom, hydroxyl group, alkyl group, haloalkyl group, alkenyl group, alkynyl group, cycloalkyl group, alkoxy group, aralkyl group, aryloxy group, aryl group, amino group, heterocyclic group having a nitrogen atom which nitrogen atom is a ring-membered hetero atom and bonds to the nitrogen atom in the above formula (3), cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group or halogen atom.
• This R 2 is the same as the group explained for the above hetero ring. That is, Y is the same as X in the hetero ring represented by the above formula (2).
• Y are the same as those enumerated for X.
• "m" indicating the number of Y's is preferably 0 or 1 from the viewpoints of double peak characteristic and fading speed, particularly preferably 0 from the viewpoint of double peak characteristic.
• R 10 , R 11 , R 12 and R 13 are each independently a hydrogen atom, hydroxyl group, alkyl group, haloalkyl group, alkenyl group, alkynyl group, cycloalkyl group, alkoxy group, aralkyl group, aryloxy group, aryl group, amino group, heterocyclic group having a nitrogen atom as a member hetero atom and bonded to a carbon atom bonded thereto via the nitrogen atom, cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group or halogen atom.
• alkyl group, haloalkyl group, alkenyl group, alkynyl group, cycloalkyl group, alkoxy group, aralkyl group, aryloxy group, aryl group, amino group, heterocyclic group having a nitrogen atom as a member hetero atom and bonded to a carbon atom bonded thereto via the nitrogen atom, alkylcarbonyl group, alkoxycarbonyl group and halogen atom are the same as those enumerated for the group R 2 .
• R 10 and R 11 , or R 12 and R 13 may be bonded together to form a carbonyl group or aliphatic hydrocarbon ring together with the carbon atom bonded thereto.
• the aliphatic hydrocarbon ring formed by bonding together R 10 and R 11 , or R 12 and R 13 is preferably an aliphatic hydrocarbon ring having 3 to 10 carbon atoms as exemplified by cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring and cyclooctane ring.
• One or more hydrogen atoms on the aliphatic hydrocarbon ring may be substituted by the above alkyl group, haloalkyl group, alkoxy group or halogen atom.
• R 10 and R 10 (1 ⁇ 0 and 1), R 10 and R 12 (1 ⁇ 0 and n ⁇ 0) or R 12 and R 12 (n ⁇ 0 and 1) may be bonded together to form an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring together with a carbon atom bonded thereto.
• adjacent R 10 and R 10 (1 ⁇ 0 and 1) or adjacent R 12 and R 12 (n ⁇ 0 and 1) may be bonded together to form an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring together with a carbon atom bonded thereto.
• the aliphatic hydrocarbon ring formed by bonding together adjacent R 10 and R 10 , R 10 and R 12 , or R 12 and R 12 is preferably an aliphatic hydrocarbon ring having 3 to 10 carbon atoms as exemplified by cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring and cyclooctane ring.
• One or more hydrogen atoms on the aliphatic hydrocarbon ring may be substituted by the above alkyl group, haloalkyl group, alkoxy group or halogen atom.
• the aromatic hydrocarbon ring formed by bonding together adjacent R 10 and R 10 , R 10 and R 12 , or R 12 and R 12 is preferably an aromatic hydrocarbon ring having 6 to 14 carbon atoms as exemplified by benzene ring and naphthalene ring.
• One or more hydrogen atoms on the aliphatic hydrocarbon ring may be substituted by the above alkyl group, haloalkyl group, alkoxy group or halogen atom.
• R 10 to R 13 include hydrogen atom, alkyl group, haloalkyl group, alkoxy group and halogen atom, and R 10 and R 11 , or R 12 and R 13 are bonded together to form a carbonyl group together with a carbon atom bonded thereto.
• R 10 and R 11 are each preferably a hydrogen atom, alkyl group or alkoxy group from the viewpoint of double peak characteristic, as exemplified by hydrogen atom, methyl group and methoxy group.
• R 12 and R 13 are each preferably a hydrogen atom, haloalkyl group or halogen atom from the viewpoint of double peak characteristic, and R 10 and R 11 , or R 12 and R 13 are preferably bonded together to form a carbonyl group together with a carbon atom bonded thereto, as exemplified by hydrogen atom, trifluoromethyl group, fluorine atom and carbonyl group.
• (1+m+n) is preferably 2 to 3 from the viewpoints of fading speed and double peak characteristic.
• (1+m+n) is particularly preferably 2 from the viewpoint of fading speed and 3 from the viewpoint of double peak characteristic.
• hetero ring represented by the above formula (2) Particularly preferred examples of the hetero ring represented by the above formula (2) are given below.
• carbon atoms denoted by 7 and 8 are 7-position and 8-position carbon atoms in the above formula (1), respectively.
• chromene compound of the present invention has an indenonaphthopyran skeleton as represented by the above formula (1) or (5) and the above groups as the 6-position, 7-position and 8-position substitutes, it exhibit excellent photochromic properties. Therefore, although substituents at other positions are not particularly limited, the following chromene compound having other substituents is particularly preferred as the chromene compound having excellent photochromic properties. A description is subsequently given of this preferred chromene compound.
• chromene compounds having a skeleton represented by the above formula (1) a chromene compound represented by the following formula (6) is preferred.
• R 1 the ring portion represented by the following formula and X are as defined in the above formula (1).
• Other groups will be described hereinbelow.
• the 5-position substituent R 3 is a hydrogen atom, hydroxyl group, alkyl group, haloalkyl group, alkenyl group, alkynyl group, cycloalkyl group, alkoxy group, aralkyl group, aryloxy group, aryl group, amino group, heterocyclic group having a nitrogen atom which nitrogen atom is a ring-membered hetero atom and bonds to the 5-positon carbon atom, cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group or halogen atom.
• alkyl group, haloalkyl group, alkenyl group, alkynyl group, cycloalkyl group, alkoxy group, aralkyl group, aryloxy group, aryl group, amino group, heterocyclic group having a nitrogen atom which nitrogen atom is a ring-membered hetero atom and bonds to the 5-positon carbon atom, alkylcarbonyl group, alkoxycarbonyl group and halogen atom are the same as those enumerated for the group R 2
• the group R 3 is involved in fading speed.
• R 3 preferably has a stereoscopically small substituent.
• the group R 3 is particularly preferably a hydrogen atom.
• the 9- to 12-position substituent R 4 is a hydroxyl group, alkyl group, haloalkyl group, alkenyl group, alkynyl group, cycloalkyl group, alkoxy group, aralkyl group, aryloxy group, aryl group, amino group, heterocyclic group having a nitrogen atom as a member hetero atom and bonded to a benzene ring bonded thereto via the nitrogen atom, cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group or halogen atom.
• alkyl group, haloalkyl group, alkenyl group, alkynyl group, cycloalkyl group, alkoxy group, aralkyl group, aryloxy group, aryl group, amino group, heterocyclic group having a nitrogen atom as a member hetero atom and bonded to a benzene ring bonded thereto via the nitrogen atom, alkylcarbonyl group, alkoxycarbonyl group and halogen atom are the same as those enumerated for the group R 2 .
• R 4 ' s denotes the number of R 4 ' s and an integer of 0 to 4. When “a” is 2 or more, R 4 ' s may be the same or different.
• the group R 4 is involved in fading speed.
• the group R 4 is preferably an electron absorbing group.
• the group R 4 is an electron absorbing group, it is preferably bonded to the 11-position carbon atom so as to accelerate the fading speed.
• the particularly preferred electron absorbing group is a cyano group or haloalkyl group, more specifically, cyano group or trifluoromethyl group.
• R 5 and R 3 are each independently a hydroxyl group, alkyl group, haloalkyl group, alkenyl group, alkynyl group, cycloalkyl group, alkoxy group, aralkyl group, aryloxy group, aryl group, amino group, heterocyclic group having a nitrogen atom as a member hetero atom and bonded to a benzene ring bonded thereto via the nitrogen atom, cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group or halogen atom.
• alkyl group, haloalkyl group, alkenyl group, alkynyl group, cycloalkyl group, alkoxy group, aralkyl group, aryloxy group, aryl group, amino group, heterocyclic group having a nitrogen atom as a member hetero atom and bonded to a benzene ring bonded thereto via the nitrogen atom, alkylcarbonyl group, alkoxycarbonyl group and halogen atom are the same as those enumerated for the group R 2 .
• R 5 ' s and R 6 ' s denote the numbers of the substituents R 5 ' s and R 6 ' s, respectively, and are each independently an integer of 0 to 5.
• R 5 ' s and R 6 ' s may be the same or different.
• the substituents R 5 and R 6 are involved in double peak characteristic and fading speed.
• the numbers and positions of the substituents are not particularly limited, they are preferably existent at the p-position of a benzene ring bonded thereto in order to enhance the double peak characteristic and obtain a high fading speed.
• the preferred substituents are each an alkyl group, alkoxy group, amino group or heterocyclic group having a nitrogen atom as a member hetero atom and bonded to a benzene bonded thereto via the nitrogen atom, as exemplified by hydrogen atom, methyl group, methoxy group, dimethylamino group and morpholino group.
• the substituents are each preferably a hydrogen atom, alkyl group, alkoxy group or heterocyclic group having a nitrogen atom as a member hetero atom and bonded to a benzene ring bonded thereto via the nitrogen atom, as exemplified by hydrogen atom, methyl group, methoxy group and morpholino group.
• the 13-position groups R 7 and R 8 are each independently a hydrogen atom, hydroxyl group, alkyl group, haloalkyl group, alkenyl group, alkynyl group, cycloalkyl group, alkoxy group, aralkyl group, aryloxy group, aryl group, amino group, heterocyclic group having a nitrogen atom as a member hetero atom and bonded to the 13-position carbon atom via the nitrogen atom, cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group or halogen atom.
• alkyl group, haloalkyl group, alkenyl group, alkynyl group, cycloalkyl group, alkoxy group, aralkyl group, aryloxy group, aryl group, amino group, heterocyclic group having a nitrogen atom as a member hetero atom and bonded to the 13-position carbon atom via the nitrogen atom, alkylcarbonyl group, alkoxycarbonyl group and halogen atom are the same as those enumerated for the group R 2
• R 7 and R 8 may be bonded together to form a carbonyl group or aliphatic hydrocarbon ring together with the 13-position carbon atom.
• the number of member carbon atoms of the aliphatic hydrocarbon ring is preferably 4 to 20, more preferably 4 to 15 from the viewpoints of color optical density and fading speed. From the viewpoint of fading speed, the number of member carbon atoms is particular preferably 4 to 12.
• This aliphatic hydrocarbon ring may have at least one substituent selected from alkyl group, haloalkyl group, cycloalkyl group, alkoxy group, amino group, aralkyl group, aryl group and halogen atom.
• alkyl group Preferred examples of the alkyl group, haloalkyl group, cycloalkyl group, alkoxy group, amino group, aralkyl group, aryl group and halogen atom as substituents are the same as those enumerated for the group R 2 . Out of these, an alkyl group is preferred from the viewpoints of color optical density and fading speed, as exemplified by methyl group.
• preferred substituents R 7 and R 8 are each selected from alkyl group, alkoxy group and hydroxyl group, and R 7 and R 8 are bonded together to form an aliphatic hydrocarbon ring together with the 13-position carbon atom.
• An example of the alkyl group is a methyl group
• an example of the alkoxy group is a methoxy group.
• R 7 and R 8 are preferably bonded together to form an aliphatic hydrocarbon ring together with the 13-position carbon atom so as to reduce color development by heat at room temperature under no exposure to light (this color development will be referred to as "initial coloration due to thermochromism” hereinafter) and accelerate the fading speed while retaining the double peak characteristic.
• the aliphatic hydrocarbon ring is preferably a single ring having 4 to 20 member carbon atoms, bicyclo ring or tricyclo ring.
• aliphatic hydrocarbon ring examples include single rings such as cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring and 3,3,5,5-tetramethylcyclohexane ring, bicyclo rings such as bicyclo[2,2,1]heptane ring, bicyclo[3,2,1]octane ring and bioyclo[3,3,1]nonane ring, and tricyclo rings such as adamantane ring.
• single rings such as cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring and 3,3,5,5-tetramethylcyclohexan
• a single ring formed by bonding together the groups R 7 and R 8 exhibits a particularly excellent effect.
• Specific examples of the single ring include cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring and 3,3,5,5-tetramethylcyclohexane ring.
• cyclooctane ring and 3,3,5,5-tetramethylcyclohexane ring are particularly preferred.
• the hetero ring including 7-position, 8-position and X is preferably a 5- to 7-membered hetero ring represented by the above formula (4).
• the chromene compound is represented by the following formula (7).
• R 1 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , "a", "b” and “c” are as defined in the above formula (6), and the ring portion represented by the following formula and X, Y, R 10 , R 11 , R 12 , R 13 , "l", “m” and “n” are as defined in the above formula (5).
• chromene compound is the following compounds.
• the chromene compound of the present invention is existent as an achromatic or light yellow solid or viscous liquid at normal temperature and normal pressure and can be confirmed by the following means (1) to (3).
• the production process of the chromene compound of the present invention is not particularly limited, and any synthesis process may be employed. As a typical process which is advantageously employed, a corresponding naphthol compound and a corresponding propargyl alcohol compound are reacted with each other. An example of the production process of the chromene compound represented by the above formula (6) will be described hereinbelow.
• the chromene compound represented by the above formula (6) can be advantageously produced by reacting a naphthol compound represented by the following formula (8) with a propargyl alcohol represented by the following formula (9) in the presence of an acid catalyst.
• a R 1 , R 3 , R 4 , R 7 , R 8 and the ring portion including X are as defined in the above formula (6)
• b R 3 , R 4 , R 7 , R 8 and the ring portion including X are as defined in the above formula (6)
• “b”, “c”, R 5 and R 6 are as defined in the above formula (6)
• the naphthol compound represented by the above formula (8) is provided as a novel compound by the present invention.
• "a", R 1 , R 3 , R 4 , R 7 , R 8 and the ring portion including X are as defined in the above formula (6). Therefore, it should be understood that the above explanation of the formula (6) is directly applied to these groups and the portion.
• naphthol compound represented by the above formula (8) are the following compounds.
• Ordinary naphthol compounds can be synthesized in accordance with a reaction method described in, for example, Journal of Organic Chemistry 69(10)3282-3293; 2004 , Synthetic Communications 23(16)2241-2249 (1993 ) and WO01/60881 .
• a benzene compound represented by the following formula (10) may be purchased as a reagent or may be synthesized based on the following documents.
• X, R 1 and R 3 are as defined in the above formula (2), the above formula (1) and the above formula (6).
• a benzene compound represented by the following formula (11) can be synthesized in accordance with a reaction method described in Synthesis. (10). 839-840; 1986 and Journal of Heterocyclic Chemistry, 26(4). 957-964; 1989 .
• a benzene compound represented by the following formula (12) can be synthesized in accordance with a reaction method described in Synthesis. (15). 2249-2272; 2007 , Chemical Communications. (32). 3747-3749; 2008 and Helvetica Chemica Acta. 85. (2). 442-450; 2002 .
• a benzene compound represented by the following formula (13) can be synthesized in accordance with a reaction method described in Tetrahedron Letters, 46 (12). 2071-2074; 2005 and Organic Process Research & Development 5(6). 604-608; 2001 .
• the carboxylic acid is converted into an amine by a method such as Curtius rearrangement, Hofmann rearrangement or Lossen rearrangement, and a diazonium salt is prepared from the amine.
• This diazonium salt is converted into a bromide by a Sandmeyer reaction or the like, and the obtained bromide is reacted with magnesium or lithium to prepare an organic metal reagent.
• R 4 and "a" in the above formulas (14) to (16) are as defined in the above formula (6).
• This organic metal reagent is reacted with a ketone represented by the following formula (17) at -80 to 70°C in an organic solvent for 10 minutes to 4 hours to obtain an alcohol material represented by the following formula (18).
• R 7 and R 8 in the above formula (17) are as defined in the above formula (6))
• the naphthol compound of interest can be synthesized by carrying out the Friedel-Crafts reaction of this alcohol material at 10 to 120°C for 10 minutes to 2 hours under a neutral to acid condition.
• the reaction ratio of the above organic metal reagent to the ketone represented by the above formula (17) is selected from among a wide range but generally selected from a range of 1:10 to 10:1 (molar ratio).
• the reaction temperature is preferably -80 to 70°C, and an aprotic organic solvent such as diethyl ether, tetrahydrofuran, benzene or toluene is used as the solvent.
• the naphthol compound represented by the above formula (8) can be obtained by carrying out the Friedel-Crafts reaction of the alcohol material in the neutral to acid condition.
• the acid catalyst is preferably selected from acetic acid, hydrochloric acid, sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid and acid alumina.
• the acid catalyst is preferably used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the alcohol material.
• a solvent such as tetrahydrofuran, benzene or toluene is used.
• the naphthol compound of the present invention is existent as an achromatic or light yellow solid or viscous liquid at normal temperature and normal pressure and can be confirmed by the following means (1) to (3).
• the propargyl alcohol compound represented by the above formula (9) is an already known compound.
• the propargyl alcohol compound can be synthesized, for example, by reacting a benzophenone compound corresponding to the above formula (9) with a metal acetylene compound such as lithium acetylide.
• the reaction ratio of the naphthol compound to the propargyl alcohol compound is selected from among a range of 1:10 to 10:1 (molar ratio).
• the acid catalyst is used sulfuric acid, benzenesulfonic acid, p-toluenesulfonic acid or acid alumina.
• the acid catalyst is used in an amount of 0.1 to 10 pars by weight based on 100 parts by weight of the total of the naphthol compound and the propargyl alcohol compound.
• the reaction temperature is preferably 0 to 200°C.
• An aprotic organic solvent such as N-methylpyrrolidone, dimethyl formamide, tetrahydrofuran, benzene or toluene is preferably used as the solvent.
• the method of purifying the product obtained through the above reaction is not particularly limited.
• the obtained product may be purified by carrying out silica gel column purification and further recrystallization.
• the chromene compound of the present invention Since the chromene compound of the present invention has high double peak characteristic, when it is mixed with another photochromic compound to prepare a photochromic composition which develops a brown or grey color, the amount of the photochromic compound which develops a yellow color and has low durability can be reduced, and a color change at the time of fading and a color change at the time of deterioration hardly occur. Further, since the chromene compound has little initial coloration, an optical article containing the chromene compound of the present invention, for example, a photochromic lens containing the chromene compound of the present invention has high transparency under no exposure to light.
• the photochromic compound to be mixed with the chromene compound of the present invention so as to adjust the color is a known compound.
• this photochromic compound include chromene compounds described in WO01/060811 and JP-A 2009-67680 .
• the chromene compound of the present invention exhibits excellent photochromic properties as described above.
• a polymer material dispersion of the chromene compound of the present invention is most practical, and a photochromic optical article having a polymer molded product containing the chromene compound of the present invention dispersed therein as a constituent member exhibits excellent photochromic properties. Therefore, the chromene compound of the present invention can be used especially in photochromic lenses (optical articles).
• a lens is obtained by a method known per se, capable of obtaining uniform light controllability.
• a method in which a thermoplastic resin and the chromene compound of the present invention are mixed together in a molten state to form a lens is employed.
• a method in which a polymer film containing the chromene compound of the present invention dispersed uniformly therein is formed on the surface of a lens, or a method in which the chromene compound of the present invention is dissolved, for example, in silicone oil and impregnated into the surface of a lens at 150 to 200°C for 10 to 60 minutes is also employed.
• the chromene compound is dispersed into the surface portion of the lens as described above, the surface of the lens may be further coated with a curable substance as required to obtain a photochromic lens.
• a method in which a photochromic curable composition containing the chromene compound of the present invention and a polymerizable monomer is polymerized by a predetermined method to obtain a lens may be employed.
• a photochromic lens can be formed directly by polymerizing the curable composition by a known method.
• the photochromic curable composition may be applied to a plastic lens (optical substrate) and polymerized and cured to form a polymer film containing the chromene compound of the present invention dispersed therein on the optical substrate, thereby obtaining a photochromic lens (optical article) (this method may be referred to as "coating method").
• the surface of the polymer film may be further coated with a curable substance.
• the polymerizable monomer in use is not particularly limited, known polymerizable monomers may be used, and a combination of known polymerizable monomers may be selected according to the desired performance of an optical article.
• the 13 C-nuclear magnetic resonance spectrum when the 13 C-nuclear magnetic resonance spectrum was measured, it showed a peak based on the carbon of an aromatic ring at ⁇ of around 110 to 160 ppm, a peak based on the carbon of an alkyleneoxy group at ⁇ of around 80 to 140 ppm and peaks based on the carbons of an alkyl group and an alkoxy group at ⁇ of around 20 to 80 ppm.
• the chromene compound obtained in the above example was mixed with a photopolymerization initiator and a polymerizable monomer, the resulting mixture was applied to the surface of a lens substrate, and ultraviolet light was applied to polymerize the coating film on the surface of the lens substrate.
• a photochromic curable composition prepared by mixing together 50 parts by mass of 2,2-bis(4-methacryloyloxypentaethoxyphenyl)propane, 10 parts by mass of polyethylene glycol diacrylate (average molecular weight of 532), 10 parts by mass of trimethylolpropane trimethacrylate, 10 parts by mass of polyester oligomer hexaacrylate (EB-1830 of Daicel UCB Co., Ltd.) and 10 parts by mass of glycidyl methacrylate was used as radical polymerizable monomers.
• the photochromic curable composition obtained by the above method was applied to the surface of a lens substrate (CR39: acrylic resin plastic lens; refractive index of 1.50) by using the 1H-DX2 spin coater of MIKASA Co., Ltd.
• This coated lens was irradiated with light of a metal halide lamp having an output of 120 mW/cm 2 in a nitrogen gas atmosphere for 3 minutes to cure the photochromic curable composition so as to produce an optical article coated with a polymer film containing the chromene compound dispersed therein (thickness of polymer film: 40 ⁇ m) (photochromic plastic lens).
• Photochromic plastic lenses were manufactured and their characteristic properties were evaluated in the same manner as in Example 6 except that the compounds obtained in Examples 2 to 5 were used as the chromene compound. The results are shown in Table 3.
• the compound Nos. 1 to 5 are chromene compounds obtained in Examples 1 to 5, respectively.
• Example 6 For comparison, the operation of Example 6 was repeated by using the compound of the following formula (A) (Comparative Example 1), the compound of the following formula (B) (Comparative Example 2), the compound of the following formula (C) (Comparative Example 3), the compound of the following formula (D) (Comparative Example 4), the compound of the following formula (E) (Comparative Example 5), the compound of the following formula (F) (Comparative Example 6), the compound of the following formula (G) (Comparative Example 7) and the compound of the following formula (H) (Comparative Example 8).
• the chromene compounds used in these comparative examples are given below.
• Photochromic plastic lenses were obtained by using the above chromene compounds and their photochromic properties were evaluated in the same manner as in Example 6. The results are shown in Table 4.
• Table 4 Comparative Example No. Compound No. ⁇ max Color optical density Double peak characteristic Fading half period Initial coloration (absorption end) Initial coloration (thermochromism) Residual rate (nm) A 0 A Y /A B ⁇ 1/2 (sec) (nm) (%) (A 50 /A 0 ) X100 1 A 457 0.69 1.56 195 397 67 76 574 0.45 196 75 77 2 B 475 0.26 0.80 140 404 77 69 585 0.32 140 77 69 3 C 470 0.25 0.64 116 411 78 68 580 0.39 116 78 68 4 D 455 0.30 0.94 83 410 77 35 576 0.32 83 78 35 5 E 485 0.28 0.84 83 418 74 69 595 0.37 83 74 70 6 F
• Comparative Example 1 Although color optical density and double peak characteristic are satisfactory, initial coloration due to thermochromism is large and the fading speed is low. In Comparative Examples 2, 3, 4, 5, 7 and 8, since the double peak characteristic is low, color control is not satisfactory when a photochromic plastic lens having a color of a neutral tint is to be manufactured. In Comparative Example 6, although color optical density and double peak characteristic are satisfactory, initial coloration is large as the absorption end goes beyond 420 nm into a visible range.
• Chromene compounds shown in Table 5 were synthesized in the same manner as in Example 1. When the structures of the obtained chromene compounds were analyzed in the same manner as in Example 1, it was confirmed that they were compounds represented by the structural formulas shown in Table 5. Table 6 shows the elemental analysis values and 1 H spectral values of the chromene compounds obtained in Examples. In Table 6, the compound Nos. 11 to 51 are chromene compounds obtained in Examples 11 to 51, respectively. Table 5 Ex. No.
• Photochromic plastic lenses were manufactured and their characteristic properties were evaluated in the same manner as in Example 6 except that the compounds obtained in Examples 11 to 51 were used as chromene compounds. The results are shown in Table 7. In Table 7, compound Nos. 11 to 51 are chromene compounds obtained in Examples 11 to 51, respectively. Table 7 Example No. Compound No.
• the bromo material of the above formula (23) was dissolved in 900 ml of N,N-dimethylformamide and cooled with ice, and8.1g (202.5 mmol) of sodium hydroxide (60 % in oil) was added and stirred for 1 hour. After agitation, 28.7 g (202.5 mmol) of methyl iodide was added and stirred at room temperature for 5 hours. After the reaction, the reaction product was washed in water, the solvent was removed, and the obtained product was purified by column chromatography to obtain an anisole material represented by the following formula (24) as 45.4 g (176.7 mmol, yield of 96 %) of orange oil.
• the acetyl material of the above formula (27) was dispersed into 80 ml of methanol. 300 ml of an aqueous solution of 35.6 g (891.0 mmol) of sodium hydroxide was added to this solution and refluxed for 3 hours. After the reaction, the reaction product was washed with concentrated hydrochloric acid and then with water, the solvent was removed, and the obtained product was purified by reslurrying with toluene to obtain a hydroxycarboxylic acid derivative represented by the following formula (28) as 16.2 g (44.6 mmol, yield rate of 90 %) of a yellow solid.
• the dibenzyl material of the above formula (29) was dispersed into 150 ml of isopropyl alcohol. 120 ml of an aqueous solution of 26.2 g (655.5 mmol) of sodium hydroxide was added to this solution and refluxed for 3 hours. After the reaction, the reaction product was washed with concentrated hydrochloric acid and then with water, the solvent was removed, and the obtained product was purified by reslurrying with toluene to obtain a benzyloxycarboxylic acid derivative represented by the following formula (30) as 17.3 g (38.0 mmol, yield rate of 87 %) of a yellow solid.
• the benzyloxycarboxylic acid derivative of the above formula (30) was dispersed into 350 ml of toluene. 11.5 (114.0 mmol) of triethylamine and 13.6 g (49.4 mmol) of diphenylphosphorylazide were added to this solution and stirred at room temperature for 2 hours. 8.8 g (190.0 mmol) of ethanol was added to this solution to carry out a reaction at 70°C for 2 hours. Thereafter, 100 ml of ethanol was added to this solution, and then 21.3 g (380.0 mmol) of potassium hydroxide was added and refluxed for 5 hours.
• the amino material of the above formula (31) was dispersed into 500 ml of acetonitrile, and 120g (190.0 mmol) of a 6 % hydrochloric acid aqueous solution was added to the dispersion and cooled to 0 to 5°C. 23.6 g (114.0 mmol) of a 33 % sodium nitrite aqueous solution was added to this solution and stirred for 30 minutes. 66.1 g (190.0 mmol) of a 50 % potassium iodide aqueous solution was added to this solution and stirred at room temperature for 5 hours.
• the iodine material of the above formula (32) was dispersed into 600 ml of toluene and cooled to -30°C. 20.6 ml (32.9 mmol) of n-butyl lithium (1. 6M hexane solution) was added dropwise to this solution and stirred for 30 minutes. 10.6 ml of a toluene solution of 5.3 g (34.3 mmol) of 3,3,5,5-tetramethylcyclohexanone was added dropwise to this solution and stirred at 0 °C for 3 hours.
• the ketone adduct of the above formula (33) was dissolved in 200 ml of tetrahydrofuran, and 4.5 (71.2 mmol) of ammonium formate and 5 g of 5 % palladium carbide were added and stirred at room temperature for 8 hours. After the reaction, toluene was added, the reaction product was washed in water, the solvent was removed, and the obtained product was purified by reslurrying with toluene to obtain a debenzylated material represented by the following formula (34) as 7.6 g (16.0 mmol, yield rate of 90 %) of a yellow solid.
• the debenzylated material of the above formula (34) was dissolved in 150 ml of toluene and heated to 90°C. 9.1 g (48.0 mmol) of p-toluensulfonic acid was added to this solution and refluxed for 3 hours. After the reaction, the reaction product was washed in water, and the solvent was removed to obtain a naphthol material represented by the following formula (35) as 5.7 g (12.5 mmol, yield rate of 78 %) of a yellow solid.
• the 13 C-nuclear magnetic resonance spectrum when the 13 C-nuclear magnetic resonance spectrum was measured, it showed a peak based on the carbon of an aromatic ring at ⁇ of around 110 to 160 ppm, a peak based on the carbon of an alkyleneoxy group at ⁇ of around 80 to 140 ppm, and peaks based on the carbons of an alkyl group and an alkoxy group at ⁇ of around 20 to 80 ppm.
• This compound is a naphthol compound used in the above Example 20.
• Naphthol compounds shown in the table were synthesized in the same manner as in Example 93.
• the structures of the obtained products were analyzed by using the same structure confirming means as in Example 93, it was confirmed that they were naphthol compounds used in Examples shown in Table 8.
• Table 8 shows the elemental analysis values of these compounds and the calculated values and characteristic 1 H-NMR spectra obtained from the structural formulas of the compounds.
• Table 8 Example No. Examples of chromene compounds* No.
• the chromene compound of the present invention develops a color of a neutral tint by itself, it can be used alone and hardly undergoes a color change at the time of fading and a color change at the time of deterioration. Further, since it has little initial coloration, high color optical density, high double peak characteristic and high fading speed, an extremely excellent photochromic lens can be obtained from the chromene compound. Therefore, color can be controlled by mixing it with another photochromic compound, and even when it is mixed with another photochromic compound, it can exhibit excellent photochromic properties.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Optics & Photonics (AREA)
• General Physics & Mathematics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Plural Heterocyclic Compounds (AREA)
• Pyrane Compounds (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
• Nitrogen Condensed Heterocyclic Rings (AREA)
• Eyeglasses (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=43386672

Family Applications (1)

Country Status (10)

Cited By (2)

Families Citing this family (5)

Citations (2)

Family Cites Families (5)

• 2010
  • 2010-06-22 US US13/379,809 patent/US20120145974A1/en not_active Abandoned
  • 2010-06-22 CN CN2010800181026A patent/CN102414214A/zh active Pending
  • 2010-06-22 SG SG2011093937A patent/SG176911A1/en unknown
  • 2010-06-22 EP EP10792222A patent/EP2447267A4/fr not_active Withdrawn
  • 2010-06-22 JP JP2011519960A patent/JPWO2010150905A1/ja not_active Withdrawn
  • 2010-06-22 AU AU2010263533A patent/AU2010263533A1/en not_active Abandoned
  • 2010-06-22 WO PCT/JP2010/060936 patent/WO2010150905A1/fr active Application Filing
  • 2010-06-22 MX MX2011013281A patent/MX2011013281A/es not_active Application Discontinuation
  • 2010-06-22 BR BRPI1012249A patent/BRPI1012249A2/pt not_active IP Right Cessation
  • 2010-06-22 KR KR1020117024541A patent/KR20120098402A/ko not_active Application Discontinuation

Patent Citations (2)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events